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1.
Chromium (VI) which exists in many industrial wastewater is considered highly toxic. The aim of the present investigation was to study the reduction of chromium (VI) to chromium (III) and then removing it with the help of weathered basalt andesite products. Reduction of the chromium (VI) to chromium (III) by hydrazinium sulfate was investigated. The influence of hydronium ion concentration, contact time, hydrazinium sulphate dosage and temperature has been tested in batch runs. The process was found to be acid, temperature and concentration dependent. The suitability of weathered basalt andesite products as a potential sorbent was assessed for the removal of chromium (III) following batch mode of operation. The effect of various parameters such as hydronium ion concentration, shaking time, sorbent dose, initial metal ion concentration and temperature on the removal of chromium (III) from aqueous solution was studied. Thermodynamic parameters (?H°, ?S° and ?G°) for the sorption process were evaluated. Analysis of sorption obtained results showed that the sorption pattern followed the Freundlich, Langmuir and Dubinin-Kaganer-Radushkevich isotherms. The process follows pseudo second order rate and surface diffusion is identified as the predominating mechanism. The sorption process was shown to be reversible by the recovery of sorbed chromium (III) upon extraction with 0.5 M nitric acid. The sorbent, before and after sorption, was characterized by fourier transform infrared spectrometer, X-ray diffraction, scanning electron microscope, transmision electron microscope and thermogravimetric analyse methodes. An increase in crystallanity after sorption of chromium was observed. An industrial effluent was successfully treated with the same sorbent with convincing results.  相似文献   

2.
This study reports the potential ability of non-living biomass of Cabomba caroliniana for biosorption of Cr(III) and Cr(VI) from aqueous solutions. Effects of contact time, biosorbent dosage, pH of the medium, initial concentration of metal ion and protonation of the biosorbent on heavy metal–biosorbent interactions were studied through batch sorption experiments. Cr(III) was sorbed more rapidly than Cr(VI) and the pH of the medium significantly affected the extent of biosorption of the two metal species differently. Surface titrations showed that the surface of the biosorbent is positively charged at low pH while it is negatively charged at pH higher than 4.0. Protonation of the biosorbent increased its capacity for removal of Cr(III), while decreasing that of Cr(VI). FT-IR spectra of the biosorbent confirmed the involvement of –OH groups on the biosorbent surface in the chromium removal process. Kinetic and equilibrium data showed that the sorption process of each chromium species followed pseudo second-order kinetic model and both Langmuir and Freundlich isothermal models. A possible mechanism for the biosorption of chromium species by non-living C. caroliniana is suggested.  相似文献   

3.
This paper presents the removal of hazardous hexavalent chromium from liquid waste streams using divinylbenzene copolymer resin Amberlite IRA 96. Important sorption parameters such as contact time, pH, resin dosage and initial metal concentration were studied at 30?°C. The kinetic study was conducted using pseudo-first and pseudo-second-order kinetics at 30?°C. The sorption process was found to be pH dependent. Maximum removal was obtained at pH 2 under optimized conditions. The sorption process was rapid and 99?% of the removal was achieved in first 30?min. The equilibrium data were fitted to both Langmuir and Freundlich models. The better regression coefficient (R 2) in Freundlich model suggests the multilayer sorption process. The value of Gibbs free energy for sorption process was found to be ?12.394?kJmol?1. The negative value indicated the spontaneity of the sorption process. Scanning electron microscope and energy dispersive X-ray spectroscopy studies were conducted to find the role of surface morphology during sorption process. The Fourier transform infrared study was conducted to identify the functional groups responsible for interaction between the resin and chromium. Desorption and regeneration studies were also carried out.  相似文献   

4.
Aluminium smelters are major sources of F emission to the environment. We studied, in laboratory experiments, the sorption and desorption of fluoride on organic and mineral horizons of soils located within 2 km from one of these factories, situated in the northern coast of Galicia (NW Spain). The soils, developed from granite, are acid (pH H2O 3.9–5.5), rich in organic matter (4–16 % C in the A horizon) and most A horizons have high Al saturation in the exchange complex. All samples showed a notable F sorption, between 1,066 and 1,589 mg kg?1, after adding 200 mg F L?1, which accounts for 53–80 % of F added. The sorption was slightly higher in the A horizons than in the respective organic horizons (differences of up to 194 mg kg?1). The fluoride sorption upon addition of 200 mg F L?1 correlated significantly (p < 0.05) with soil pH in water (r = ?0.77), iron extracted by acid ammonium oxalate (r = 0.68), aluminium plus iron extracted by acid ammonium oxalate (r = 0.63), exchange aluminium (r = 0.52) and clay percentage in soil (r = 0.76). The F sorption fitted to both Langmuir and Freundlich models. Desorbed F accounted for only 12–22 % of sorbed fluoride and correlated (p < 0.05) negatively with non-crystalline (extracted by acid ammonium oxalate) Fe (r = ?0.51) and clay content (r = ?0.74) and positively with organic matter (r = 0.69) and with the effective cation exchange capacity of the soil (r = 0.50).  相似文献   

5.
The effect of citrate and oxalate on tremolite dissolution rate was measured at 37 °C in non-stirred flow-through reactors, using modified Gamble’s solutions at pH 4 (macrophages), 7.4 (interstitial fluids) and 5.5 (intermediate check point) containing 0, 0.15, 1.5 and 15 mmol L−1 of citrate or oxalate. The dissolution rates calculated from Si concentration in the output solutions without organic ligands depend on pH, decreasing when the pH increases from −13.00 (pH 4) to −13.35 (pH 7.4) mol g−1 s−1 and following a proton-promoted mechanism. The presence of both ligands enhances dissolution rates at every pH, increasing this effect when the ligand concentration increases. Citrate produces a stronger effect as a catalyst than oxalate, mainly at more acidic pHs and enhances dissolution rates until 20 times for solutions with 15 mmol L−1 citrate. However, at pH 7.4 the effect is lighter and oxalate solutions (15 mmol L−1) only enhances dissolution rates eight times respect to free organic ligand solutions. Dissolution is promoted by the attack to protons and organic ligands to the tremolite surface. Magnesium speciation in oxalate and citrate solutions shows that Mg citrate complexes are more effective than oxalate ones during the alteration of tremolite in magrophages, but this tendency is the opposite for interstitial fluids, being oxalate magnesium complexes stronger. The biodurability estimations show that the destruction of the fibers is faster in acidic conditions (macrophages) than in the neutral solutions (interstitial fluid). At pH 4, both ligands oxalate and citrate reduce the residence time of the fibers with respect to that calculated in absence of ligands. Nevertheless, at pH 7.4 the presence of ligands does not reduce significantly the lifetime of the fibers.  相似文献   

6.
Considerable fractions of the Hg content of lake and river systems in Scandinavia are discharged from the soil of the catchments. An important soil type in Scandinavia is the iron–humus podzol. The sorption characteristics of this soil type for inorganic Hg(II) and monomethyl mercury were investigated by batch experiments. The solubility of Hg2+ and CH3Hg+ in the soil horizons containing organic matter increases with increasing pH of the soil solution by favoring the formation of solute organic matter–mercury complexes. While the solubility of Hg2+ is strongly dependent on complexation to dissolved organic matter, the solubility of CH3Hg+ is more dependent on ion exchange. The concentration of solute inorganic Hg(II) increased with increasing temperature probably because of an increase in the concentration of dissolved organic carbon. There was no effect of temperature on the concentration of solute CH3Hg+. At pH values where inorganic mercury–hydroxo complexes are formed, inorganic Hg(II) is efficiently sorbed to the metal oxides of the mineral soil. The soil–water distributions of inorganic Hg(II) in the different soil horizons were described by Freundlich isotherms or linear isotherms for common and contaminated mercury contents in the soils.  相似文献   

7.
Barium ion cross-linked alginate beads have shown great affinity to toxic hexavalent chromium ions in aqueous solution, in contrast to the traditionally used calcium alginate beads. Our adsorption experiments were carried out by the batch contact method. The optimal pH for removal was found to be pH 4. The equilibrium was established in 4 h, and the removal efficiency of chromium(VI) was found to be 95 %. The adsorption data were applied to Langmuir, Freundlich, Dubinin–Redushkevich (D–R), and Temkin isotherm equations. Both Langmuir and Freundlich isotherm constants indicated a favorable adsorption. The value of mean sorption energy calculated from D–R isoterm indicates that the adsorption is essentially physical. The high maximum chromium(VI) adsorption capacity was determined from the Langmuir isotherm as 36.5 mg/g dry alginate beads. The chromium(VI) adsorption data were analyzed using several kinetic models such as the pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models, and the rate constants were quantified. Our study suggests that barium alginate beads can be used as cost-effective and efficient adsorbents for the removal of chromium(VI) from contaminated waters.  相似文献   

8.
Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The Kd (L g−1) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.  相似文献   

9.
Sorption of the organic pollutant 4-nitrophenol (4-NP) by pyrolyzed and activated Jordanian oil-shale was studied. Pyrolyzed oil shale was prepared using a fluidized bed reactor at 520 °C in the presence of nitrogen. Physical activation was carried out by treating the pyrolyzed oil shale with CO2 at 830 °C, while chemical activation was achieved by using KOH and ZnCl2 as impregnating agents. Batch kinetics and isotherm studies were conducted to evaluate the sorption process. Effects of contact time, initial sorbate concentration, sorbent concentration, temperature, pH and inorganic salts (NaCl and KCl) on the sorption process by the different sorbents were considered. Chemically activated oil shale, pretreated with ZnCl2, gave the highest uptake of 4-NP. The isotherm experimental data fit reasonably well to Langmuir, Freundlich and Redlich-Paterson models. Three kinetic models, namely the Morris-Weber, Lagergren, and Pseudo-Second-Order model (PSOM), were applied to represent the experimental results for both pyrolyzed and ZnCl2-oil shale sorbents.  相似文献   

10.
Brucite (Mg(OH)2) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H2PO4− > catechol ≥ HCO3− > ascorbate > citrate > oxalate > acetate ∼ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO43−, CO32−, F−, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO42− and B(OH)4− with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation.The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.  相似文献   

11.
《Geochimica et cosmochimica acta》1999,63(19-20):3205-3215
Sorption processes typically control trace metal concentrations in aquatic systems. To illustrate the impact of various types of surface sites on metal ion sorption behavior, Co(II) and Sr(II) sorption by several clay minerals under a range pH and background electrolyte conditions was studied. X-ray absorption spectroscopy (XAS) was used to characterize the surface complexes formed to explain the basis for the sorption trends. At low pH, Co(II) could be displaced from the surface by increasing the Na ion concentration. XAS analysis of these samples showed that sorbed Co(II) retained the coordination structure of aqueous phase Co(II), suggesting the formation of weakly associated, outer-sphere, mononuclear Co complexes at permanent charge sites. At high pH, sorbed Co could not be displaced by increasing the Na ion concentration. The XAS analyses of these samples indicated the formation of Co coprecipitates. The results of the Sr(II) sorption experiments suggested weaker bonding between sorbed Sr and the solid surfaces, regardless of solution conditions and adsorbent. XAS analysis of Sr sorption samples revealed the formation of mononuclear, outer-sphere complexes of Sr at clay–water interfaces, similar to the outer-sphere Co sorption samples observed only at low pH.  相似文献   

12.
Thermodynamic properties of 32 dissolved thorium species and 9 thorium-bearing solid phases have been collected from the literature, critically evaluated and estimated where necessary for 25°C and 1 atm pressure. Although the data are incomplete, especially for thorium minerals and organic complexes, some tentative conclusions can be drawn. Dissolved thorium is almost invariably complexed in natural waters. For example, based on ligand concentrations typical of ground water (ΣCl = 10 ppm, ΣF = 0.3 ppm, ΣSO4 = 100 ppm, andΣPO4 = 0.1 ppm), the predominant thorium species are Th(SO4)02, ThF2+2, and Th(HPO4)20below pH ≈ 4.5; Th(HPO4)2?3 from about pH 4.5 to 7.5; and Th(OH)04 above pH 7.5. Based on stability constants for thorium citrate, oxalate and EDTA complexes, it seems likely that organic complexes predominate over inorganic complexes of thorium in organic-rich stream waters, swamp waters, soil horizons, and waterlogged recent sediments. The thorium dissolved in seawater is probably present in organic complexes and as Th(OH)04. The tendency for thorium to form strong complexes enhances its potential for transport in natural waters by many orders of magnitude below pH 7 in the case of inorganic complexing, and below about pH 8 when organic complexing is important. The existence of complexes in addition to those formed with hydroxyl, is apparent from the fact that measured dissolved thorium in fresh surface waters (pH values generally 5–8) usually ranges from about 0.01 to 1 ppb and in surface seawater (pH = 8.1) is about 0.00064 ppb. This may be contrasted with the computed solubility of thorianite in pure water which is only 0.00001 ppb Th as Th(OH)04 above pH 5. Although complexing increases the solubility of thorium-bearing heavy minerals below pH 8, maximum thorium concentrations in natural waters are probably limited in general by the paucity and slow solution rate of these minerals and by sorption processes, rather than by mineral-solution equilibria.  相似文献   

13.
Migration of uranium and arsenic in aquatic environments is often controlled by sorption on minerals present along the water flow path. To investigate the sorption behaviour, batch experiments were conducted for uranium and arsenic as single components and also solutions containing both uranium and arsenic in the presence of SiO2, Al2O3, TiO2 and FeOOH at a pH ranging from 3 to 9. In solutions containing only U(VI) or As(V) with the minerals, the sorption of U(VI) was low at acidic pH range and increases with increasing pH, whereas As(V) showed opposite sorption behaviour to Al2O3, TiO2 and FeOOH from acidic pH range to alkaline condition. For the As(V)–SiO2 system, the sorption was low for almost all pH. Sorption of U(VI) and As(V) on SiO2 and FeOOH is almost similar in solutions containing either U(VI) or As(V) separately, or both together. In the U(VI)–As(V)–Al2O3 system, a significant retardation in uranyl sorption and an enhancement in arsenate sorption on Al2O3 were observed for a wide range of pH. The sorption behaviour of U(VI) and As(V) was changed when Al2O3 was replaced by TiO2, where an increase in sorption was observed for both elements. The sorption behaviour of uranyl and arsenate in the U(VI)–As(V)–TiO2 system gives evidence for the formation of uranyl–arsenate complexes. The change in sorption retardation/enhancement of U(VI) and As(V) could be explained by the formation of uranyl–arsenate complexes or due to the competitive sorption between uranyl and arsenate species.  相似文献   

14.
Interactions of copper, organic acids, and sulfate in goethite suspensions   总被引：1，自引：0，他引：1  
Sorption of copper and sulfate onto goethite (-FeOOH) in aqueous solution is examined in Cu---SO4 binary-sorbate systems and in Cu-SO4-organic acid (either phthalic acid or chelidamic acid) ternary-sorbate systems. Compared to single-sorbate systems, sorption of Cu onto goethite was enhanced at low pH values in the presence of sulfate. Sorption data for Cu and SO4 in Cu---SO4 binary-sorbate systems were described with the Generalized Two Layer Model by proposing formation of a Cu---SO4 ternary surface complex. Addition of sulfate to a Cu-phthalic acid binary sorbate system had little effect on Cu sorption. However, addition of sulfate to Cu-chelidamic acid binary-sorbate systems resulted in significant reduction of Cu sorption at low pH values, primarily due to competition for surface sites between sulfate and Cu-chelidamic acid ternary surface complexes. While organic acids such as humic substances can potentially influence sorption of metal ions, results from this study suggest that the extent of such influence may be strongly dependent on the presence of other sorbing anions, such as sulfate. Sorption of Cu and SO4 in Cu---SO4-organic acid ternary-sorbate systems was predicted reasonably well, based on surface reactions and equilibrium constants derived from fitting of sorption data from single- and binary-sorbate systems. These modeling results provide a validation of the extrapolation of sorption from simple systems to multicomponent systems through surface complexation modeling.  相似文献   

15.
The biosorption of chromium (VI) ions from aqueous solutions by two adsorbents viz. mango and neem sawdust was studied under a batch mode. An initial pH of 2.0 was most favorable for chromium (VI) removal by both the adsorbents. The results obtained for the final concentration of chromium (VI) and chromium (DI) at a pH range of 2–8 indicated that a combined effect of biosorption and reduction was involved in the chromium (VI) removal specially when the pH value is lower than 3. The maximum loading capacity was calculated from adsorption isotherms by applying the Langmuir model and found to be higher for neem sawdust (58.82 mg/g). Evaluation of experimental data in terms of biosorption kinetics showed that the biosorption of chromium (VI) by neem sawdust followed pseudo second-order kinetics. Therefore, the rate limiting step may be chemical sorption or chemisorption. The efficiency of this process was examined in using tannery wastewater contaminated with chromium (VI) ions in column mode.  相似文献   

16.
The charged sites on soil particles are important for the retention/adsorption of metals. Metallic counterions can neutralize the intrinsic charges on the surfaces of soil particles by forming complexes. In this study, efforts have been made to determine the effect of surface potential, pH, and ionic strength on the adsorption of four metal ions, hexavalent chromium Cr(VI), trivalent chromium Cr(III), nickel Ni(II) and cadmium Cd(II), in glacial till soil. Batch tests were performed to determine the effect of pH (2–12) and ionic strength (0.001–0.1 M KCl) on zeta potential of the glacial till soil. The point of zero charge (pH PZC ) of glacial till was found to be 7.0±2.5. Surface charge experiments revealed the high buffering capacity of the glacial till. Batch adsorption experiments were conducted at natural pH (8.2) using various concentrations of selected metals. The adsorption data was described by the Freundlich adsorption model. Overall glacial till shows lower adsorption affinity to Cr(VI) as compared to cationic metals, Cr(III), Ni(II) and Cd(II).  相似文献   

17.
The goal of this study is examination of the mixture between adsorption and permeation process for removing chromium (VI) from the water. Two types of supported membranes are developed: The first one which was made by sol–gel method is called nanoporous and the second one which was made by electrospinning is called nanofiber. The sorption capacity of nanoporous and nanofiber is examined in single batch experiments at various pH values, and it is found that maximum chromium removal is observed for both nanoporous and nanofiber at pH 3.5. Adsorption studies illustrated that the Cr(VI) adsorption onto alumina nanoporous and nanofiber is affected by changes in pH, contact time, dosage of adsorbent, concentration of chromium and solution volume. Langmuir and Freundlich isotherms can be used to explain the adsorption equilibria of Cr(VI) onto alumina nanoporous and nanofiber. It was found that balance adsorption data adequate Langmuir isotherm more than Freundlich model. Adsorption kinetics was found to be fitted to pseudo-second order and Weber and Morris model. The output of multiple linear regressions was run for the second-order response surface model implied that the linear agents of pH, sorbent dosage and Cr(VI) concentration are more significant factors. Manufacturing electrospun alumina nanofiber and sol–gel nanoporous with these cheap materials, renewable and fast methods are so important although the removal percentage is significant.  相似文献   

18.
Sorption of radionuclides onto stable colloids can significantly enhance their transport in groundwater. Batch adsorption studies were performed to evaluate the influence of various experimental parameters like initial pH, contact time, temperature and concentration of Na+ and Ca2+ ions on the sorption of Cs on clay. The sorption process is dependent on pH of the solution with distribution coefficient (K d) found to increase with increase in pH. The kinetic experiments were carried out at different temperatures, and the results have shown that the sorption process fits well into a pseudo-second-order mechanism with apparent activation energy of 45.7?kJ/mol. The rate constant was found to decrease with increase in temperature. The thermodynamic parameters such as ?G 0, ?H 0 and ?S 0 were calculated. The negative value of ?H 0 indicates that the reaction is exothermic. The negative values obtained for ?G 0 indicated that the sorption of cesium on clay was spontaneous at all studied concentrations. The distribution coefficient was found to decrease with increasing concentration of Na+ and Ca2+ ions. The cesium sorption data were fitted to Freundlich, Langmuir, Temkin and Dubinin–Radushkevich (D–R) isotherms. The values of Langmuir separation factor (R L) indicate a favorable Cs adsorption. The values of mean free energy of sorption (E) at various temperatures ranged from 10.5 to 11.1?kJ/mol, which indicates that the sorption process follows chemisorption.  相似文献   

19.
Elevated polycyclic aromatic hydrocarbon (PAH) concentrations were determined in different Chinese coals, with the highest concentrations in bituminous coals. Phenanthrene (Phen) was chosen as the probe compound for PAHs to study the sorption behavior of coal. No native Phen was detected in desorption experiments indicating irreversible sorption–desorption behavior of PAHs in raw coal samples. Sorption mechanism was further studied under varying conditions of pH value and ionic strength. Different ranks of coal showed different sorption behavior under acidic, neutral, and alkaline conditions. Batch experiments were further processed for the selected coals at pH values from 3 to 11 at a constant aqueous concentration. Sorption capacities of all coals decreased with increased pH except for YJ coal. Furthermore, although DOC-associated Phen mass contributed little to the total Phen mass under different pH values, the significant negative correlations between M DOC and log K OC values were observed for all coal samples, indicating a significant role played by DOC in the coal sorption. In addition, sorption experiments under varying ionic strength showed that the ionic strength influence was more obvious in sorption isotherms for higher rank coals with increasing ionic strength, and this effect was most significant when ionic strength increased from 0 to 0.15 M, especially at relatively low aqueous concentrations.  相似文献   

20.
Sorption of Cm(III) and Eu(III) at trace concentrations onto Ca-montmorillonite (SWy-1) and Na-illite (Illite du Puy) has been studied under anaerobic conditions by batch sorption experiments and time-resolved laser fluorescence spectroscopy (TRLFS). Comparison of the results from spectroscopic and batch sorption experiments with Cm and Eu indicates the existence of outer-sphere complexes at pH <4 in the experiments with Na-illite (0.25 g/L solid; 2.5 × 10−7 mol/L Cm; 0.1 mol/L NaClO4). In the case of Ca-montmorillonite, (0.25 g/L solid, 2.5 × 10−7 mol/L Cm or 10−6 mol/L Eu, 0.066 mol/L Ca(ClO4)2), Cm/Eu outer-sphere complexes do not form at significant levels due to the Ca2+ competition for the clay mineral cation-exchange sites. TRLFS spectra indicate the formation of inner-sphere surface complexes at pH >5 for both clay minerals. Five H2O/OH− molecules remain in the first metal ion coordination sphere of the sorbed Eu/Cm. Measured fluorescence lifetimes of sorbed Eu/Cm and peak deconvolution of Cm-spectra are consistent with the formation of surface complexes of the form ≡S-O-Eu/Cm(OH)x(2−x)(H2O)5−x. At pH ≥ 12 Cm becomes incorporated into a surface precipitate at the Ca-montmorillonite surface presumably composed of Ca(OH)2 or calcium silicate hydrate. A dramatic shift of the fluorescence emission band by more than 20 nm and a clear increase in the fluorescence lifetime suggests the almost complete displacement of coordinated H2O and OH−. The pH dependent Eu sorption data obtained in batch experiments are consistent with spectroscopic data on Eu and Cm within experimental uncertainties thus demonstrating the validity of Eu as a homologue for trivalent actinides. Parameterization of a two-site protolysis nonelectrostatic surface complexation and cation exchange model using the batch sorption data and spectroscopic results is discussed in Part 2 of this work.  相似文献   

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